Salts of morpholino-(2,3 b) phenox azonium and hair dye and hair setting lotion compositions containing the same

ABSTRACT

Novel salts of morpholino-(2,3-b)phenoxazonium are prepared by condensing a substituted paranitrosoaniline and a 6-hydroxy phenomorpholine. The novel salts are incorporated into hair dye and hair setting lotion compositions.

United States Patent Bugaut et al.

SALTS OF MORPHOLINO-(23-MPHEN- OXAZONIUM AND HAIR DYE AND HAIR SETTINGLOTION COMPOSITIONS CONTAINING THE SAME Inventors: Andree Bugaut,Boulogne-sur-Seine;

Monique Laudon, Gagny. both of France Assignee: LOreal, Paris, FranceFiled: Jan. 30, 1973 Appl. No.: 328,091

Related US. Application Data Division of Ser. No. l65 740, July 23.1971, Pat. Nov 3,824.074.

Foreign Application Priority Data July 31, 1970 Luxembourg 61452 US. Cl260/242; 260/37 R; 260/246 R; 260/244 R; 8/10; 8/179 July 22, 1975 Int.Cl .4 C09!) 19/00 Field of Search 260/246, 242

References Cited UNITED STATES PATENTS 4/l968 Braun 260/246 PrimaryExaminer-Harry J. Moatz Attorney. Agent, or FirmCushman Darby & Cushman2 Claims, No Drawings 1 2 SALTS OF MORPHOLINO-(2,3 B) PI-IENOX and (b) ao-hydroxy phenomorpholine having the for- AZONIUM AND HAIR DYE AND HAIRSETTING mula:

LOTION COMPOSITIONS CONTAINING THE SAME s 1 1 This is a division, ofapplication Ser. No. 165,740 filed July 23, 1971, now U.S. Pat.3,824,074. N

The present invention relates to salts of morpholino- (2,3-b)phenoxazonium having formula ,1

N /n l2\ 1 6 3 N 4 0 5/ N R 1 wherein R, is selected from the groupconsisting of hywherein 1 to s have the meanings indicated ove. drogenand lower alkyl having l-4 carbon atoms, According to a first method ofpreparing the com- R, and R each independently are selected from thepounds of this invention equimolecular amounts of a group consisting ofalkyl having l-4 carbon atoms, hyparanitroso-aniline of formula (11) andof a o-hydroxy droxylalkyl having 14 carbon atoms, Carbamylalkylphcnomorpholine of formula (III) are heated under rehaving 1-4 carbonatoms, w-aminoalkyl having 1-4 flux in absolute ethanol, in the presenceof an excess of Carbon ammsa d i kl l h i 1-4 carbon anhydrous zincchloride. The product obtained is a atoms wherein the amino moiety isacylated with a double zinc and indamine chloride having the formula:

monocarboxylic organic acid having the formula R'- which is separatedfrom the reaction mixture by filtra- COOl-l wherein R is selected fromthe group consisting tion. Generally, the reaction is effected atambient of alkyl having l-4 carbon atoms and phenyl or pressure and theanhydrous zinc chloride is present wherein said amino moiety is monoordi-substituted usually in amounts ranging from about 1 to 1.5 mole withalkyl having 1-4 carbon atoms, 01' wher n h niper mole ofparanitrosoaniline or phenomorpholine. trogen of said amino moiety isincluded in a heterocycle selected from the group consisting ofmorpholinyl This compound of formula (IV) is, after isolation and andpiperidinyl, and Xrepresents a member selected washing in an alcoholsuch as a lower alkanol, cyclized from the group consisting of Cl", Br,C10,, and by reflux heating in a mixture of dimethylformamide C1 Zn itbeing understood that these salts can be pres and acetic acid, thedevelopment of the reaction being ent in a tautomeric form of thatrepresented by the followed by chromatography. Once the cyclization isabove formula and that in the case in which R or R completed, thereaction mixture is diluted in water and represents an w-aminoalkyl, theamine function can be thereafter, filtered. Acid having the formula XHsalified by an acid having the formula HX wherein X wherein X has themeaning given above, or a water solhas the meaning given above. ublesalt thereof is then added to the filtration product The above compoundscan be obtained in accorin amounts sufficient to precipitate thephenoxazonium dance with two methods using as initial reactants (a) asalt of formula (I), which then is isolated by filtration.

substituted paranitrosoaniline having the formula:

A second process for the production of the com pounds of formula (1)comprises reflux heating in an R alcoholic medium, such as a loweralkanol, either (a) NO a salt, such as the hydrochloride or thehydrobromide, N of a paranitrosoaniline of formula (11) with a o-hydroxy(11) phenomorpholine of formula ([11), or (b) a paranitrosoaniline offormula (ll) with a salt, such as the hy drochloride or thehydrobromide, of a 6-hydroxy phenomorpholine of formula (111). In thisalternate pro cess, the nitrosated derivative of formula (II) isgenerally used in the proportion of l to 1.5 moles per mole of compound(lll). Generally, the reaction is carried out at ambient pressure. Thedevelopment of the reaction is followed by chromatography, and once thecyclization is completed. the resulting reaction mixture is filteredhot. In certain cases, the phenoxazonium chloride or bromidecrystallizes upon cooling of the filtrate. It is then separated byfiltration and transformed, if necessary, into the desired phenoxazoniumsalt. In the other cases, either an acid having the formula HX where Xhas the meaning given above or a watersoluble salt thereof is added tothe filtrate, diluted or not with water.

The compounds of formula (1) constitute dyes of a remarkable ability forthe dyeing of keratinous fibers, in particular human hair. They exhibitgreat solubility in water and in alcohol, such as lower alkanols andthey exhibit great dyeing power within a wide pH range, for instance,from about 4.5 to 11.

Consequently, the present invention also relates to a novel dyeingcomposition for keratinous fibers, in particular human hair, comprisingan aqueous solution containing at least one compound of formula (I).

The dyeing compositions according to the invention can contain only thecompounds of formula (I), in which case it is found that they impart towhite hair shades ranging from blue to green. Advantageously, theapplication period to achieve such results can be in the order of aboutthree minutes at room temperature, because of the exceptional affinityof the compounds of formula (I) to keratinous fibers. The shadesobtained in this manner, which are very luminous, often iridescent, andrich in shimmers or gleams, have the further advantage of masking thered in reddish-brown and auburn hair.

The exceptional affinity of the dyes of this invention for keratinicfibers, together with their excellent solubility in water and alcoholsenable these compounds to be incorporated in the compositions accordingto the invention in extremely small concentrations, which can varybetween 0.0005 to 1% in weight and preferably between 0.001 and 0.5% byweight of the composition.

The pH of said compositions generally ranges between about 4.5 and 11and preferably between and 10.

Further, the compositions according to the invention can also containother direct dyes, for example, azo dyes, anthraquinone dyes, nitro dyesof the benzene series, indoanilines, indophenols, indamines or otherknown phenoxazonium salts.

The dyeing Compositions according to the invention are generally in theform of aqueous or aqueous alcoholic solution which can be preparedeasily by dissolving in water or in a mixture of water and alcohol oneor more of the compounds of formula (I), mixed or not mixed with otherdirect dyes. The compositions can also contain thickeners and be in theform of creams or gels. Generally lower alkanols such as ethanol andisopropanol are used to form the aqueous alco holic solutions, with thealcohol being present in amounts ranging from about l to 50 weightpercent of the total dye composition.

Further, the compositions according to the invention can also containvarious ingredients normally used in cosmetics, for example, wettingagents, dispersing agents, swelling agents, penetrating agents,emollients or perfumes. They can also be packaged in aerosol cans orcontainers under pressure using conventional aerosol propellants such asthe chlorofluorohydrocarbons including dichlorodifluoromethane,trichloromonofluoromethane and their mixtures.

The dying of keratinous fibers, in particular human hair, by means ofthe dyeing compositions according to the invention, is effected in aconventional manner by applying the composition on the fibers to bedyed, with which it is allowed to remain in contact for a period varyingbetween 3 and 30 minutes, said application being followed by rinsing thefibers and by eventually washing and drying the fibers.

The dyes according to the invention can also be used in the form ofcapillary hair setting lotions.

Thus the present invention also relates to a hair setting lotioncomposition comprising an aqueous alcoholic solution containing at leastone cosmetic filmforming resin and at least one compound of formula Theproportion of the compound of formula (I) in the hair setting lotionsaccording to the invention can be extremely small. This proportiongenerally varies between 0.005 and 1% in weight and preferably between0.001 and 0.5% by weight of the total composition.

Representative cosmetic film-forming resins which can be used in thehair setting lotion composition of this invention include, for instance,polyvinylpyrrolidone having a molecular weight ranging from about 10,000to 700,000, the vinyl acetate-crotonic acid copolymers having amolecular weight of about 40,000 to 200,000 wherein the ratio of VA/CAis preferably about 90/10; vinylpyrrolidone-vinyl acetate co polymerswherein the ratio of PVP to VA ranges between 30/70 and /30 and whichhave a molecular weight ranging between about 40,000 to 160,000; maleicanhydride-butylvinyl ether copolymers, etc. These resins are usedgenerally in an amount from about 1 to 3% by weight of the totalcomposition.

Representative alcohols suitable for the production of the hair settinglotion compositions of this invention are the low molecular weightalcohols, and preferably ethanol or isopropanol, and they are presentgenerally in amounts ranging from about 20 to 50% by weight of the saidcomposition.

The pH of the hair setting lotion composition can vary between about4.5-11, and, preferably, between about 5l0.

The hair setting lotion compositions of this invention which containonly dyes of formula (I) constitute tinting compositions which impartextremely luminous glints to the hair and which cover up or mask the redof auburn or reddish-brown hair.

These hair setting lotion compositions can also contam other directdyes, for example. azo dyes or anthraqumone dyes, nitro dyes of thebenzene series, indoanilines, indophenols, indamines or otherphenoxazonium salts.

EXAMPLE I 4-methyl S-diethylamino morpholino (2,3-b) phenoxazoniumperchlorate is prepared as follows:

To a dispersion of 0.045 mole (9.65 g) of paranitroso N,N-diethylanilinehydrochloride in 35 cc of 96 ethanol, there is added 0.03 mole (4.95 g)of 4-methyl 6- hydroxy phenomorpholine. The resulting alcoholic solutionis reflux heated for L5 hours and then hot filtered. To the filtratethere are added 35 cc of water, and a resulting very light browninsoluble substance is then eliminated by filtering the reaction mediumagain. After addition of sodium perchlorate to the hydroalcoholicsolution, the expected phenoxazonium perchlorate precipitates and isrecovered by filtration yielding about 5 grams thereof. After washingthe recovered product with a little ice water and then with ethanol, itmelts with decomposition at 235. The product thus obtained ischromatographically pure.

Calculated for C 10 CIN 3 a EXAMPLE 2 4-methyl 8-dibutylarninomorpholino (2,3-b) phenoxazonium perchlorate is prepared as follows:

To 35 cc of absolute ethanol there are added 0.045 mole (l2.l7 g) ofp-nitroso N,N-dibutylaniline hydrochloride and 0.03 mole (4.95 g) of4-methyl G-hydroxy phenomorpholine. The resulting alcoholic solution isbrought to reflux for one hour and a half and then hot filtered. cc ofwater are then added to the filtrate and the reaction mixture is againfiltered to eliminate a resulting brown insoluble material. Afteraddition of sodium perchlorate to the aqueous alcoholic solution. theexpected phenoxazonium perchlorate precipitates and is removed byfiltration, yielding about 4.6 g of the same which. afterrecrystallization in methanol, melts with decomposition at l8l.

Calculated for Found Analysis 1=i mN.,0..Ci

EXAMPLE 3 0.045 mole (l5 g.) of p-nitroso N,N-(B-piperidinoethyl,ethyl)aniline dihydrochloride and 0.03 mole (4.95 g) of 4-methyl o-hydroxyphenomorpholine are added to 60 cc of 96 ethanol. The resultingalcoholic solution is reflux heated for one hour and hot filtered. Thencc of water are added to the filtrate. After addition of 70% perchloricacid to the hydroalcoholic solution, the above expected phenoxazoniumdiperchlorate precipi tates and is removed therefrom by filtration,yielding about 8 g of the same which is then washed with ethanol. Theresulting product is chromatographically pure and melts withdecomposition at 249.

morpholino (2.3-b) phenoxazonium perchlorate is prepared as follows;

1\ CH CH l 3 i F NH-CO- 0.03 mole g) of p-nitroso N,N-(B-benzoylaminoethyl, ethyl) aniline hydrochloride and 0.02 mole (3.3 g) of4-methyl o-hydroxy phenomorpholine are added to cc of 96 ethanol. Theresulting alcoholic solution is heated to reflux for one hour. It isthen hot filtered and lOO cc of water are added to the filtrate. Theresulting mixture is then filtered again to eliminate a light browninsoluble contained therein.

After addition of 70% perchloric acid to the aqueous alcoholic solution,the phenoxazonium perchlorate precipitates and is removed by filtrationyielding about 6 g of the same which is then washed with a little icewater. After crystallization in cc of 96 ethanol. the product ischromatographically pure and melts with de composition at l57.

OH-CI-L-CH.

a 0 \II n v C -Crl On CH 2 Analysis Calculated for 'Found an st 1 t ca57.51 57.12 51.20 H92 i 4.97 i 5.09 5.06 N7r g [0.33 i032 10.38 CW: 6 616.48 6.44

' EXAMPLE 5 4-methyl 8-di-B-hydroxyethylamino morpholino (2,3-b)phenoxazonium perchlorate is prepared as follows:

To 60 cc of 96 ethanol there are added 0.03 mole (7.39 g) of p nitrosoN.N-di-B-hydroxyethylaniline hy -amino 25 drochloride and 0.02 mole (3.3g) of 4-methyl 6- hydroxy phenornorpholine. The resulting solution isheated to reflux for one hour and then cooled. 60 cc of water and 3 ccof perchloric acid are then added, thus precipitating the abovephenoxazonium perchlorate which is then filtered, yielding about 3.5 gof the same which melts with decomposition between 263 and 265.

This product is chromatographically pure.

Analysis Calculated for Found C tli n ii fl C7r 50.05 50.20 50.38 H%4.82 4.97 4.92 N% 9.22 9.36 9.34 Cl7v 7.79 7.85 7.90

EX AM PLE 6 4-methyl S-di-B-hydroxyethylamino r'horpholino (2.3-b)phenoxazonium chloride is prepared as follows:

To 25 cc of absolute ethanol there are added 0.03 mole (7.39 g) ofp-nitroso N,N-di-B- hydroxyethylamino hydrochloride and 0.02 mole (3.3g) of N-methyl fi-hydroxy phenomorpholine. The resulting solution isheated to reflux for 1 hour, and it is then cooled to The abovephenoxazonium chlo ride precipitates and is filtered therefrom, yieldingabout 3.5 g of the same which, after recrystallization in adioxane-acetic acid mixture, is chromatographically pure and is in theform of bronze green crystals.

EXAMPLE 7 8-(B-piperidinoethy, ethyl) -amino morpholino (2.3- b)phenoxazonium diperchlorate is prepared as follows:

about 8.5 g of the same which, after recrystallization in a mixture ofdimethylformamide and methanol, is chromatographically pure and meltswith decomposition between 232 and 234.

Analysis Calculated for Found C% 46.54 46.86 46.73 H% 5.05 5.15 5.17 N%9.44 9.64 9.67

EXAMPLE 8 The double chloride of zinc and 4-methyl 8- dibutylaminomorpholino (2,3-b) phenoxazonium is prepared as follows:

. H9 t\ Q To 40 cc of ethanol at 96 there are added 0.045 mole (l2.l7 g)of p-nitroso N.N-dibutylaniline hydro chloride and 0.03 mole (4.95 g) ofN-methyl o-hydroxy phenomorpholine. The resulting solution is heated toreflux for one hour and then hot filtered. 100 cc of water are added tothe filtrate which is then filtered to eliminate a light brown insolublecontained therein. Zinc chloride is then added to the aqueous alcoholicsolution which is cooled in ice. The above zinc and phenoxazonium doublechloride precipitates and is filtered therefrom. washed with a littleice water and recrystallized in ethanol. The product obtained ischromatographically pure and is in the form of bronze crystals.

EXAMPLE 9 An alternate process for the preparation of the 4- methyl8-diethylamino morpholino (2,3-b) phenoxazonium perchlorate described inExample 1 is as fol lows:

To 30 cc of absolute ethanol, there are added 0.03 mole (5.34 g) ofp-nitroso N.N-diethylaniline, 0.03 mole (4.95 g) of N-methyl o-hydroxyphenomorpholine and 4.1 g of anhydrous zinc chloride. The resultingalcohol solution is heated to reflux for one half hour. It is thencooled and the following double zinc and indamine chloride crystals offormula:

precipitates which is then recovered by filtration. yielding about 1 1grams of the same which are then washed with ethanol.

The above salt is then dissolved in 30 cc of dimethylformamide mixedwith l2 cc of acetic acid. The resulting solution is heated for one halfhour between l30 and Then 200 cc of water are added and 3.2 g of theabove zinc salt precipitate and are recovered by filtration. Sodiumperchlorate is then added to the filtrate, thus precipitating 2.8 g ofthe expected phenoxazonium perchlorate which, after recrystallization inmethanol, is chromatographically pure and melts with decomposition at235.

Cl Zn 3 EXAMPLE 10 The double chloride of zinc and 4-ethyl 8-dibutylamino morpholino (2,3-b) phenoxazonium is prepared as follows:

First phase: Preparation of the N-ethyl 6-hydroxy phenomorpholine.

L19 mole (I80 g) of -hydroxy phenomorpholine are dissolved in two litersof 1.25 N sodium hydroxide solution. This solution is heated to 5060C.There are then added to this solution in small amounts, under agitationand simultaneously, by means of two dropping funnels, on the one hand7.2 moles (580 cc) of ethyl iodide, and on the other hand 300 cc of 2Nsodium hy droxide solution. These successive additions last for l8hours, during which the reaction mixture is maintained at approximately60.

The reaction mixture is then cooled to One liter of methylisobutylketoneis then added thereto under agitation. 128 g of N,N-diethyl fi-ethoxybenzomorpholinium iodide which melts at [86 are then isolated bycentrifuging the reaction mixture. On the other hand, themethylisobutylketonic phase is separated by decantation from the aqueoussodium hydroxide phase of the filtrate. After washing with water. dryingon anhydrous sodium sulfate and dry evaporation, 145 g of N-ethyl-ethoxy phenomorpholine are obtained. (E 0.7 mm Hg)=l22l23. Bydissolving under vacuum the quaternary derivative concurrently obtained(I28 g), an additional 65 grams of Nethyl 6-ethoxy phenomorpholine areproduced.

The 210 g (1.0l mole) of N-ethy] 6-ethoxy phenomorpholine thus obtainedare than transformed into N- ethyl 6-hydroxy phenomorpholinebromohydrate by heating the same to reflux for 6 hours in 600 cc ofhydrobromic acid (d=l.78). After cooling the reaction centrifugeextraction. Molecular weight calculated for C H NO HBr: 260. Molecularweight found by potentiometric quantitative analysis in water by meansof a 0.1N sodium hydroxide solution: 261

Analysis Calculated for Found (,.,H, ,N 0 HBr CW1 46.l5 46.06 45.82 5 H%5.38 5.48 5.5l NVr 5.38 5.35 5.33

[CLZYI 0.021 mole (5.5 g) of N-ethyl o-hydroxy phenomorpholinehydrobromide is dissolved in 20 cc of water. Ammonia (22Be) is addeduntil the solution attains a pH of 7. Then the N-ethyl 6-hydroxyphenomorpholine is extracted by means of benzene. After washing thebenzene solution in water and drying on anhydrous sodium sulfate, thesolvent is elminated under vacuum and there is obtained in oily form,2.90 g of chromatographically pure N-ethyl 6-hydroxy phenomorpholine.Molecular weight calculated for c H No 179. Mo lecular weight found bypotentiometric quantitative analysis in acetic acid by means ofperchloric acid: 176. 2nd phase: Preparation of the double chloride ofzinc and 4-ethyl S-dibutylamino morpholino (2,3-b) phenoxazonium.

To 30 cc of absolute ethanol there are added 0.02 mole of N-ethylfi-hydroxy phenomorpholine (3.58 g) and 0.03 mole of p-nitrosoN,N-dibutylaniline hydrochloride (8.2 g). The solution is heated toreflux for 30 minutes. It is then hot filtered and 75 cc of water and asmall amount of animal black are added to the filtrate, which is againfiltered. Then zinc chloride is added to the cooled filtrate and thedouble salt of zinc and phenoxazonium which was expected, precipitatesand is filtered therefrom and which after recrystallization in ethanol,is chromatographically pure.

EXAMPLE l l 8-N,N-(ethyl-B-piperidinoethyl) -amino morpholino (2,3-b)phenoxazonium dibromide is prepared as follows:

medium to -30, 198 g of the desired hydrobromide, which melts withdecomposition at l, are isolated by To l8 cc of absolute ethanol thereare added 0.009 mole (3.8 g) of p-nitroso N,N-(ethyl-B- piperidinoethyl)aniline dihydrobromide and 0.006

13 14 precipitates and is centrifuged therefrom, yielding 0.0073 mole(l.5 g) of p-nitroso N.N-(carbamyl about 1.3 g of the same which afterrecrystallization in methyl, ethyl) aniline and 0.005 mole l .3 g) of4-ethyl a water-ethanol solution at 50%, is chromatographi- 6-hydroxyphenomorpholine hydrobromide are added cally pure. to 15 cc of absoluteethanol. The alcoholic solution is 5 heated to reflux for 30 minutes.After cooling and addition of 15 cc of ethyl acetate, the abovephcnoxazonium bromide precipitates and is filtered therefrom. The saidproduct melts with decomposition at l95.

Analysis Calculated for Found 2a an 4 2 '2 l0 C /r 49.81 49.78 4933Analysis Calculated for Found H% 5.41 5.43 5.47 mlhn tQi m1 10.10 9.979.99

Ca 53.69 52.97 53.21 1-1 1 5.14 4.98 5.011 Na 1253 12.53 12.71 l

EXAMPLE '2 EXAMPLE l4 4-ethyl8N,N(ethyl-B-piperidinoethyl) -amin Thefollowlng hair dye composition is prepared: h 2 3 b h d Dye of Example I0.05 g p 0 mo p enoxazomum 1 romide 1s prepare 20 walermqspv )0 g asfollows: Ammonia m 22Bc ....q.s.p. pH

i BI ""131 C H o .1 It I C H ca 2 5 l 2 CH I 2 N To cc of absoluteethanol there are added 0.0066 This hair dye composition is applied to95% naturally mole (2.79 g) of p-nitroso N,N-(ethyl-B- white hair for 10minutes at ambient temperature and piperidinoethyl) anilinedihydrobromide and 0.0044 imparts thereto after rinsing and shampooing astrong mole (0.8 g) of N-4-ethyl o-hydroxy phenomorpholine. erald greencolor.

The reaction medium is heated to reflux for one half hour. Then theexpected morpholine phenoxazonium dibromide precipitates and is filteredtherefrom, yielding about 0.9 g of the same which is then washed withEXAMPLE ethanol. After recrystallization in a 60% ethanol-water A h i dm sition is prepared as follows: solution, the above product is found tobe chromatographically pure.

Dye of Example I 0.00l g Analysis Calculated for pound Ethyl alcohol, at96 20 g O,,,H,.N.O,Br, Water. q.s.p. lOO g Ammonia. q.s.p. pH 10 C%51.55 51.25 5l.l7 H% 5.84 5.75 5.82 N% 9.62 9.50 9.61

This hair d e com osition is a lied to discolored or EXAMPLE 13 y p ppbleached hair for 10 minutes at ambient temperature4-ethyl8-(carbamylmethyl, ethyl) -amino (2,3-b) and imparts thereto,after rinsing and shampooing. a

phenoxazonium dibromide is prepared as follows: light emerald-greencoloration with iridescent glints.

N O H C Br N O \N l C H H N OC H 0 2 5 A hair setting lotion compositionis prepared as follows:

EXAMPLE l6 Dye of Example I (rotonic acid-vinyl acetate copolymcr (90%vinyl acetate. )9? crotonic acid. molecular weight 45.000 to 50.000Ethyl alcohol. at 96' Water. q.s.p.

Tricthanolaminc. q.s.p.

This hair setting lotion composition is applied to bleached hair andimparts thereto a very intense and very luminous blue-green color.

EXAMPLE l7 3 s 50 g mu g pH 7 The following hair dye composition isprepared:

Dye of Example 1 Ethyl alcohol. at 96 Water. q.s.p.

lZ aqueous lactic acid.q.s.p.

This hair dye composition is applied to hair which is 95% naturallywhite. After a period of about 5 minutes. the thus treated hair isrinsed and shampooed and the color obtained is a very slightly blueishgreen with silver glints.

EXAMPLE 18 A hair setting lotion is prepared as follows:

Dye of Example l N-[ 2.4'diamino 5 '-methoxy) phenyll benzoquinonc imineVinyl acetate-crotonic acid copolymcr molecular weight 45.000 to 50.000]

Ethyl alcohol. at 96 Water. q.s.p.

Triethanolamine, q.s.p.

This hair setting lotion is applied to bleached hair and imparts theretoan iridescent purple-chestnut coloring. 5

EXAMPLE l9 (Vinyl acetate 9(l'7r. crotonic acid lU;

The hair setting lotion composition is prepared:

Dye of Example l Vinyl acetate-crotonic acid copolymer (Vinyl acetate90%. crotonic acid [0%- molecular weight 45.000 to 50.000)

Ethyl alcohol. at 96 Water. q.s.p. Triethanolamine.q,s.p.

This hair setting lotion is applied to light brown hair and impartsthereto a dark tobacco-brown color with green glints.

EXAMPLE 20 2g 50g 100g pH7 A hair setting lotion is prepared as follows:

Dye of Example 1 N-l(4-hydroxy) phenyl] 3-amino 6-methyl benzoquinoneimine Vinyl acetate-crotonic acid copolymer (Vinyl acetate 90%. crotonicacid l0%- molecular weight 45.000 to 50.000)

Ethyl alcohol at 96 Water, q.s.p.

Triethanolamine, q.s.p.

This hair setting lotion is applied to hair which is 95% naturally whiteand imparts thereto a light bronze color with golden glints.

EXAMPLE 2l The following hair dye composition is prepared:

Dye of Example I 0.25 g

Butylglycol 5 g Lauryl alcohol oxycthylenated with 10.5 moles ofethylene oxide 5 g Water. q.s.p. 100 g This hair dye composition isapplied to 60% white hair and imparts thereto after a 20-minute contactperiod. followed by rinsing and shampooing. a malachite green color witha watered silk or moire effect.

EXAMPLE 22 A hair dye composition is prepared as follows:

Dye of Example 2 0.05 g Ethyl alcohol. 96 20 g Water. q.s p, [00 gAmmonia (22Be). q.s.p. pH l0 25 This hair dye composition is applied to95% naturally white hair, and imparts thereto after a lO-minute contactperiod. followed by rinsing and shampooing. a very luminous peacock-bluecolor.

EXAMPLE 23 The following hair setting lotion is prepared:

Dye of Example 2 0.02 g

N-[(4'-amino) phenyl-I 3-amino bmethyl benzoquinone imine 0. l5 g Vinylacetate-crotonic acid copolymer (Vinyl acetate 90%. crotonic acidl0'7o-molecular weight 45.000 to 50.000) 2 g lsopropanol alcohol 50 gWater. q.s.p. [00 g Tnethanolamine. q.s.p. pH 7 This hair setting lotioncomposition is applied to bleached hair and imparts thereto a very lightviolet tinge.

EXAMPLE 24 A hair dye composition is prepared as follows:

Dye of Example 3 0| g Ethyl alcohol. at 96 20 3 Water. q.s.p. 100 gAmmonia (22Belq.s.p. pH 10 This hair dye composition is applied tonaturally white hair and imparts thereto after a lO-minute contactperiod. followed by rinsing and shampooing, a very luminous turquoisecolor.

Ammonia (22Be), q.s.p. pH 10 This hair dye composition is applied to 95%naturally Dye of ExamphleI4 3 0.025 g N-(fi-amirioet y l-amino -nitro4-amino white hair and imparts thereto after a 20 minute benzenehydmbromide 0025 g contact period at normal temperature. followed by E hl l hoLqff 30g I I Water. q.s.p. I g rinsing and shampooing. a dark bluegrey color AIIIIIIDIIIII (2205c) IIISIIII PH I0 EXAMPLE 26 This hair dyecomposition is applied to 60% naturally A dye composltmn prepared asfollows: white hair, with which it is allowed to remain in contact for20 minutes. After rinsing and shampooing. the color obtained is verydark purplish chestnut-brown.

Dye of Example 3 0.1 g 2',4'-diamino-S 'methoxy)phenyi| l0 benzoquirioneimine 0.25 g EXAMPLE 3| Eth l alcohol. at 96 25 g I I I I Waier. q.s.p.100 g The following hair dye composition is prepared; Ammonia (22Be).q.s.p. pH Hi This hair dye composition is applied to 95% naturally vDVyeof Example 6 063]] g white hair and imparts thereto after a l5-minute af g fk z zos In pH contact period. followed by rinsing and shampooing. aP P belge colol" This hair dye composition is applied to bleached hairEXAMPLE 27 and imparts thereto after a 3-minute contact period at I I II normal temperature, followed by rinsing and shampoo- The followinghair setting lotion composition is preingI a pearly "ght green Colorpared:

EXAMPLE 32 Dye (If Example 3 0m g A hair setting lotion composition isprepared as foll(3'.5'-dimethyl 4-hydr0xy) phenyl] lOWSZ 2.6-dimethylbenzoquinone imine 0.05 g

Vinyl acetate-crotonic acid copolymer (crotonic acid 107:, vinyl acetate90% Dye of Example 5 0.1 g 'fx ggggg' g to SO'OOO g Vinylacetate-crotonic acid copolymer Wa er qs p. i 300 g (as in Example 2 9)2 g Triethariolamine q s p PH 7 Ehy] alcohol 96 50 g Water, q.s.p. I00 gTricthanolamine. qsp. pH 7 This hair setting lotion is applied tobleached hair and imparts thereto a Cornflower-blue color. This hairsetting lotion is applied to bleached hair and imparts thereto a veryluminous lively blue color.

EXAMPLE 28 A hair dye composition is prepared as follows: EXAMPLE 33 Thefollowing hair dye composition is prepared:

Dye of Example 3 00:5 g Nitroparaphenylenediamine 0.2 g 40 D f E I l 7ye 0 Jump e 0075 Ethyl alcohol. 96 40 8 Ethyl alcohol. 96 20 g 8 Water.qsp. II 100 2 Water. qsp. i0() 3 Ammonia B ).q- -p- P Aqueous lacticacid solution l%l q.s.p. pH 5 This hair dye composition is applied to95% naturally white hair and imparts thereto after a 10-minute 5 contactperiod at normal temperature, followed by a rinse and a shampoo, a veryluminous vivid yellowgreen coloration.

This hair dye composition is applied to 95% naturally white hair andimparts thereto after a 20 minute contact period at ambient temperatureand. after rinsing and shampooing, a silvery grey-green color.

EXAMPLE 34 EXAMPLE 29 I I I I A hair dye composition is prepared asfollows: The following hair setting lotion composition is prepared:

Dye of Example 8 0.15 g Ethyl alcohol, 96 20 g Water, q.s.p. I00 g Dyeof Example 4 0.05 g Vinyl acetate-crotonic acid copolymer (Crotonic acid10%. vinyl acetate 90%- I I I I I molecular weight 45.000 to 50,000) 2 gThis hair dye composition is applied to 95% naturally al zz g g whitehair and imparts thereto after a contact period of Triethanolamine.q.s.pi pH 7 20 minutes at ambient temperature and, after rinsing andshampooing. a deep emerald-green color. This hair setting lotion isapplied to bleached hair and imparts thereto a very luminousturquoise-blue color EXAMPLE 35 EXAMPLE 30 The following hair settinglotion composition is pre- A hair dye composition is prepared asfollows: d;

Dye of Example 10 0.] g Crotonic acid-vinyl acetate copolymcr (as inExample 29) 2 g Ethyl alcohol. 96 50 g Water. qspv 100 gTricthanolaminc. q.s.p. pH 7 This hair setting lotion is applied tobleached hair and imparts thereto an emerald-green color.

EXAMPLE 36 A hair setting lotion is prepared as follows:

Dyc of Example I l 0.05 g Vinyl acetate-crotonic acid copolymer (vinylacetate 90%. crotonic acid l7r molecular weight 45.000 to 50.000] 2 gEthyl alcohol. 96.q.s.p. 50 Water. qsp. [00 g Tricthanolamine. q.s.p. pH7 This hair setting lotion is applied to bleached hair and impartsthereto a pearly blue color.

EXAMPLE 37 The following hair dye composition is prepared:

Dye of Example l2 0.2 g Water. q.s.p. 100 g Ammonia (22Be) q.s.p. pH 9This hair dye composition is applied to 95% naturally white hair andafter a 10 minute contact period at room temperature, imparts thereto.after rinsing and shampooing, a very luninous blue color.

EXAMPLE 38 A hair setting lotion is prepared as follows:

Dye of Example l2 0.005 g Vinyl acetate-crotonic acid copolymer (vinylacetate 90%, crotonic acid l0%- molecular weight 45.000 to 50.000) 2 gEthyl alcohol. 96. q.s.p. 50 Water. q.s.p. I00 g Triethanolamine. qsp.pH 7 This hair setting lotion is applied to bleached hair and impartsthereto a pearly appearance with pale green glints.

EXAMPLE 39 The following hair setting lotion is prepared as fol lows:

Dye of Example 13 0.025 g Vinyl acetate-crotonic acid copolymer (vinylacetate 90%. crotonic acid 10%- molecular weight 45.000 to 50.000) 2 gEthyl alcohol. 96", q.s.p. 50 Water. q.s.p. 100 g Triethanolamine.q.s.p. pH 7 This hair setting lotion is applied to bleached hair andimparts thereto a pearly pale-green color.

What is claimed is:

l. A phenoxazonium salt having the formula N o /n i2\/ a l 4 6 3 :Nalkylwherein R and R' are selected from the group consisting of hydrogen andalkyl having l4 carbon atoms with at least one of R" and R being saidalkyl and -alkyl has 1-4 carbon atoms, w-aminoalkyl of the formual-ulkyl wherein said alkyl has 1-4 carbon atoms and u-amino alkyl of theformula ON-ulkyl wherein said alkyl has l-4 carbon atoms, and X isselected from the group consisting of Cl, Br, CIO, and Cl -,Zn and thetautomeric forms thereof.

2. A salt of claim 1 wherein at least one of R and R representw-aminoalkyl having l4 carbon atoms and wherein the terminal aminomoiety carries the anion moiety of an acid having the formula HX whereinX is selected from the group consisting of Cl, Br, ClO and Cl Zn.

1. A PHENOXAZONIUM SALT HAVING THE FORMULA
 2. A salt of claim 1 whereinat least one of R2 and R3 represent omega -aminoalkyl having 1-4 carbonatoms and wherein the terminal amino moiety carries the anion moiety ofan acid having the formula HX wherein X is selected from the groupconsisting of Cl, Br, ClO4 and Cl3Zn.